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The fluorescence excitation and dispersed fluorescence spectra of jet-cooled o- andm-toluidine were observed. Vibrational analysis of the spectra provided us with thepotentials for the internal rotation of the CH 3  group in both ground and excited states. Ino-toluidine, a large potential barrier to the internal rotation in the ground state ispractically removed in the excited state. On the other hand, a nearly free internalrotation of the CH 3  group in the ground state of m-toluidine gains a large barrier by theelectronic excitation. The great change in the barrier height upon the electronic excitation is more remarkable than that found for fluorotoluene. A close relationship between the barrier height and the   π   electron density at the ring carbon atom was found, indicating the hyperconjugation as the origin of the barrier height in the absence of sterichindrance.

laser chemistry

Internal Rotation of the Methyl Group in the Electronically Excited State: <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mi>o</mml:mi></mml:math>- and <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mi>m</mml:mi></mml:math>-Toluidine

Internal Rotation of the Methyl Group in the Electronically Excited State: o- and m-Toluidine